CN101183588A - Method of preparing magnetic hollow micro-nano ball with template of high molecule micro-nano ball - Google Patents
Method of preparing magnetic hollow micro-nano ball with template of high molecule micro-nano ball Download PDFInfo
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- CN101183588A CN101183588A CNA2007100471404A CN200710047140A CN101183588A CN 101183588 A CN101183588 A CN 101183588A CN A2007100471404 A CNA2007100471404 A CN A2007100471404A CN 200710047140 A CN200710047140 A CN 200710047140A CN 101183588 A CN101183588 A CN 101183588A
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Abstract
The invention discloses a preparation method of a magnetic hollow micro-nanometer sphere with a macromolecule micro-nanometer sphere as a template in the micro-nanometer material technical field. With a micro-nanometer sphere with negative charge on the surface as the template, through the micro-nanometer sphere surface in-situ reaction a magnetic compound sphere with magnetic nanometer particles as the shell and the template particles as the nuclear is generated; afterwards a layer of SiO2 can be coated on the sphere surface, and further through burning the template is removed to get the hollow magnetic micro-nanometer sphere. The invention has the advantages: the method has the advantages of easy doing, high efficiency, and easy scale; the particle diameter of the prepared magnetic hollow micro-nanometer sphere possess good controllability, and the thickness or the magnetic response of the magnetic shell can also be regulated according to the requirement.
Description
Technical field
The present invention relates to a kind of preparation method of micro-nano ball of micro Nano material technical field, specifically be a kind of be the method that template prepares the magnetic hollow micro-nano ball with the polymer micro-nanometer ball.
Background technology
The magnetic hollow micro-nano ball is meant that internal structure is hollow, and size is the magnetic hollow micro-nano ball that 0.05 μ m-100 μ m has magnetic responsiveness.Because it has hollow-core construction, and has the characteristic of magnetic response, therefore in biological technical field, be with a wide range of applications at aspects such as targeted therapy, control release, Magnetic Isolation especially.The method for preparing the magnetic hollow microballoon commonly used can reduce following two classes basically: a class is to be raw material with polymer and magnetic nano-particle, obtains the magnetic hollow micro-nano ball by two emulsion processes, emulsification solidification method, complex coacervation; Another kind of is to be template with the micro-nano ball, obtains one deck magnetic nano-particle by the various surface crusts that act on, and obtains the magnetic hollow micro-nano ball by removing template then.The magnetic hollow micro-nano ball particle size distribution of utilizing last class methods preparation is than broad, and particle diameter control is difficult, and size ratio should not prepare less magnetic hollow microballoon more greatly.Most typical method is utilized the magnetic hollow of self-assembly method (LBL) acquisition layer by layer micro-nano ball exactly in one class of back, at first make template microsphere alternately adsorb the magnetic microsphere and the electrolyte of opposite charges by Electrostatic Absorption, after waiting to reach requirement, the microballoon that obtains is removed template by dissolution method or sintering process can obtain the magnetic hollow micro-nano ball.The typical advantage of these class methods is exactly that the particle diameter of the micro-nano capsule of magnetic that obtains can be easy to control by regulating template size, Zhi Bei the hollow micro-nano ball magnetic power or the thickness of magnetic shell also can be well controlled simultaneously, it is very complicated that yet the shortcoming of this method maximum is exactly a technology, loaded down with trivial details, should not carry out large-scale production.
Find through literature search prior art, (patent publication No.: CN1718619) that Chinese patent " has magnetic composite microsphere of inorganic/organic core shell structure and preparation method thereof ", this patented technology utilizes the sulfonation microballoon to be template, obtains magnetic composite microsphere by generating magnetic particle in the microsphere surface original position.But this technology mainly concentrates on and prepares magnetic microsphere, does not relate to the content that obtains the magnetic hollow micro-nano ball.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, and it is the method that template prepares the magnetic hollow micro-nano ball that a kind of simple high molecular micro nanometer ball is provided.Easily operation and implementing of the present invention, also than being easier to form scale, the magnetic hollow micro-nano ball particle diameter controllability of preparation fine and thickness or magnetic response power the magnetic shell also can be regulated as requested.
The present invention is achieved through the following technical solutions, the present invention is a template with the high molecular micro nanometer ball that the surface has negative electrical charge, by generating with the magnetic nano-particle in the reaction of micro-nano ball surface in situ is shell, template particles is the magnetic microsphere of nuclear, can be at this magnetic microsphere surface parcel one deck SiO
2Further obtain the hollow magnetic micro-nano ball by burning the removal template.
The present invention is adapted to prepare the magnetic hollow micro-nano ball of micro/nano level (0.05 μ m-100 μ m).Among the present invention employed template microsphere be particle diameter at micro/nano level, the surface has the high molecular micro nanometer ball of electronegative functional group.
The high molecular micro nanometer ball material of indication can be any hydrophobic macromolecular material among the present invention, as polystyrene, polymethyl methacrylate, polyethyl methacrylate, poly (glycidyl methacrylate) etc., but is not limited to above different materials.The functional group that microsphere surface possesses is as carboxyl, anionic functional groups such as sulfonate radical.The high molecular micro nanometer ball at high temperature
The high molecular micro nanometer ball material of indication can be any hydrophobic macromolecular material among the present invention, it is characterized in that the macromolecule polymer material that at high temperature (200-1000 ℃) can decompose.
Among the present invention, prepare magnetic microsphere at the micro-nano ball surface in situ and can adopt adsorption and oxidation method or coprecipitation.
Described adsorption and oxidation method is meant: in the template microsphere aqueous solution of 1-30mg/ml, at N
2Protection absorption quality down is the Fe of 0.1 times-1.0 times of template microsphere quality
2+Ion adds a spot of alkali lye and hydrogen peroxide then under stirring condition, make [OH
-]: [Fe
2+]=2-5, the amount of hydrogen peroxide is Fe
2+-1 times of 0.67 times of mole.Behind the reaction 30min-60min, mixed solution is heated to 50 ℃-85 ℃ reaction 30min-2h, and reaction finishes the back cooling, and this mixed liquor is carried out Magnetic Isolation, the method of utilizing micro-nano hole to filter filters out the isolated magnetic particle of generation, then can obtain pure magnetic composite microsphere.
Described coprecipitation is meant: in the template microsphere aqueous solution of 1-30mg/ml, add 1: 2 Fe of mol ratio
2+, Fe
3+Salting liquid, wherein the quality of Fe is 0.1 times-1.0 times of template microsphere.And feeding N
2Behind the deoxygenation 10min-30min, under mechanical agitation (300-800rpm), drip aqueous slkali gradually, final [OH
-]: [Fe
2+]=5-10 is preferably 7-9.After dropwising reaction 10min-60min, mixed solution is heated to 50 ℃-85 ℃ reactions cools off behind the 30min-2h and get final product.Utilize magnet that the magnetic microsphere in the mixed solution is absorbed, remove supernatant, repeat 5 times-10 times, clarify until supernatant, till pH was neutrality, the method for utilizing micro-nano hole to filter filtered out the isolated magnetic particle of generation, then can obtain pure magnetic microsphere.
Among the present invention, can wrap up one deck SiO2 again after making magnetic microsphere, also can wrap up.During parcel, mainly adopt ripe St ber technology, that is: the magnetic microsphere of preparation is made into pure water or the alcoholic solution of 1-30mg/ml.Get this solution of 1ml, add the tetraethoxysilane of 1ml0.5-30mg/ml or the pure water or the alcoholic solution of tetramethoxy-silicane.Under churned mechanically condition (300-800rpm) then adds ammoniacal liquor or other weak base in solution, or sodium hydroxide solution, wherein the consumption of alkali be make the amount that finally makes 0H-1 in the system be the silane substance amount 4-8 doubly.And make reaction continue to get final product behind the 10min-8h.
Among the present invention, the alkali of use can be weak base such as ammoniacal liquor, organic amine or highly basic such as NaOH, potassium hydroxide etc.
Among the present invention, employed calcination temperature should guarantee the degraded of macromolecule template particles, and does not cause the magnetospheric performance change of template surface, can be between 300-1000 ℃, and preferably at 300-800 ℃, more preferably 300-700 ℃.Employed calcination time should guarantee the degraded fully of macromolecule template particles, and does not cause the magnetospheric performance change of template surface, can be between 5min-30h, and preferably between 20min-10h, 40min-8h more preferably.
The magnetic hollow micro-nano ball has important use and is worth in fields such as bio-medical, material design, enzyme engineerings.As being used for carrier various medicines and albumen in the bio-medical field, realize targeted therapy, and controlled release.Because it is loaded down with trivial details to have the method for preparing the magnetic hollow micro-nano ball now, be difficult to the unequal shortcoming of magnetic hollow micro-nano ball particle size distribution that scale is used or prepared, limited the large-scale production and the application of magnetic hollow micro-nano ball.
The invention provides and a kind ofly set out by the high molecular micro nanometer ball template, substep prepares the method for magnetic hollow micro-nano ball, and the size of magnetic hollow micro-nano ball mainly can be by the size of template micro-nano ball, generated in-situ magnetic particle thickness and surface parcel SiO
2Thickness control, the magnetic response power is then controlled by the thickness that is controlled at the magnetic particle that its surface generates.The inventive method is simple and easy to do, and is applied widely, has efficient height, characteristics that cost is low.Gained magnetic hollow micro-nano ball saturation magnetization can reach 40eum/g, can be used for the load of Magnetic Isolation, multiple material, is particularly useful for biomedicine field.
Description of drawings
Fig. 1 is the TEM photo of the hollow magnetic microsphere of embodiment 1 preparation
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The polystyrene microsphere that the surface of getting 0.5g diameter 5.4 μ m has sulfonate radical is dispersed in the 18ml water, and is placed in the 100ml there-necked flask, feeds N
230min removes the oxygen in the system; Get 0.6mmol.L
-1FeCl
3Be dispersed in the 5ml water, and ultrasonic 5min is uniformly dispersed it, with 0.3mmol.L
-1FeCl
2Be dispersed in the 5ml water, and ultrasonic 5min is uniformly dispersed it; With Fe
2+Solution and Fe
3+Solution is poured in the there-necked flask that fills the sulfonated polystyrene microballoon, drips the ammonia spirit of 4ml 28% behind stirring (500rpm) the absorption 15min in 3min gradually.With oil bath mixed solution is heated to 80 ℃ of afterreaction 1h behind the reaction 30min, utilizes magnet that magnetic microsphere is absorbed after the mixed solution cooling, remove supernatant, add deionized water then, repeat 3-10 time, be neutral until pH value of solution.Then with after the magnetic microsphere freeze drying that obtains.Get magnetic microsphere and heat 5h down at 500 ℃.Can obtain the magnetic hollow micro-nano ball after the taking-up.
As shown in Figure 1, the about 5.6 μ m of particle diameter of the magnetic hollow micro-nano ball that obtains by transmission electron microscope observing.The saturation magnetization of utilizing vibrating specimen magnetometer to record the magnetic hollow micro-nano ball is 40eum/g.
Embodiment 2
The poly (glycidyl methacrylate) microballoon that the surface of getting the 0.2g diameter and be 2.6 μ m has sulfonate radical is dispersed in the 20ml water, and is placed in the 100ml there-necked flask, feeds N
210min removes the oxygen in the system; Get 0.6mmol.L
-1FeCl
3Be dispersed in the 5ml water, and ultrasonic 5min is uniformly dispersed it, with 0.3mmol.L
-1FeCl
2Be dispersed in the 5ml water, and ultrasonic 5min is uniformly dispersed it; With Fe
2+Solution and Fe
3+Solution is poured in the there-necked flask that fills microballoon, drips the ammonia spirit of 4ml 28% behind stirring (300rpm) the absorption 15min in 3min gradually.With oil bath mixed solution is heated to 80 ℃ of afterreaction 2h behind the reaction 30min, utilizes magnet that magnetic microsphere is absorbed after the mixed solution cooling, remove supernatant, add deionized water then, repeat 3-10 time, be neutral until pH value of solution.Then with after the magnetic microsphere freeze drying that obtains.
Get the magnetic microsphere 0.1g for preparing above and be dispersed in the ethanolic solution of 20ml 90%, add the ammonia spirit of 2ml 28%.Under the condition that stirs (500rpm), drip the tetraethoxysilane ethanolic solution of 1ml 1g/ml then gradually.Behind stirring reaction 1h under the mixed solution normal temperature, with magnet magnetic microsphere is inhaled, then supernatant is outwelled, add deionized water once more, repeat 4-5 time and get final product.Then precipitation being carried out freeze drying preserves.
Get magnetic microsphere and heat 4h down at 500 ℃.Can obtain the magnetic hollow micro-nano ball after the taking-up.
The about 2.75 μ m of particle diameter of the magnetic hollow micro-nano ball that obtains by scanning electron microscopic observation.Utilize transmission electron microscope can observe microsphere surface and have uniform magnetic particle.The saturation magnetization of utilizing vibrating specimen magnetometer to record the magnetic hollow micro-nano ball is 36eum/g.
Embodiment 3
The poly (methyl methacrylate) micro-sphere that the surface of getting 0.15g diameter 800nm has carboxylate radical is dispersed in the 150ml water, and is placed in the 250ml there-necked flask, feeds N
230min removes the oxygen in the system; Get 0.4mmol.L
-1FeCl
3Be dispersed in the 5ml water, and ultrasonic 5min is uniformly dispersed it, with 0.2mmol.L
-1FeCl
2Be dispersed in the 5ml water, and ultrasonic 5min is uniformly dispersed it; With Fe
2+Solution and Fe
3+Solution is poured into and is filled in the there-necked flask that the surface has the carboxylate radical polystyrene microsphere, drips 10ml 1molL gradually after stirring (800rpm) absorption 15min in 3min
-1NaOH solution.With oil bath mixed solution is heated to 70 ℃ of afterreaction 1h behind the reaction 1h, utilizes magnet that magnetic microsphere is absorbed after the mixed solution cooling, remove supernatant, add deionized water then, repeat 3-10 time, be neutral until pH value of solution.The magnetic microsphere that obtains is carried out freeze drying to be preserved.
Get the magnetic microsphere 0.1g for preparing above and be dispersed in the ethanolic solution of 10ml, add the ammonia spirit of 5ml 28%.Under stirring condition, drip the 0.5ml tetramethoxy-silicane then gradually.Behind stirring reaction 1h under the mixed solution normal temperature, with magnet magnetic microsphere is inhaled, then supernatant is outwelled, add deionized water once more, repeat 4-5 time and get final product.Then precipitation being carried out freeze drying preserves.
The magnetic microsphere of getting the above-mentioned preparation of 0.05g is at N
2The following 700 ℃ of following heating 3h of protection.Can obtain the magnetic hollow micro-nano ball.
The magnetic hollow micro-nano ball that obtains by transmission electron microscope observing is a hollow-core construction.The saturation magnetization of utilizing vibrating specimen magnetometer to record the magnetic hollow micro-nano ball is 32eum/g.
Embodiment 4
The sulfonated polystyrene microballoon of getting the 0.5g diameter and be 0.5 μ m is dispersed in the 18ml water, and is placed in the 100ml there-necked flask, feeds N
2H removes the oxygen in the system; Get 1.0m mol.L
-1FeCl
2Be dispersed in the 5ml water, and ultrasonic 5min is uniformly dispersed it; With Fe
2+Solution goes into to fill in the there-necked flask of polystyrene microsphere, adds 10% NaOH1.2ml behind stirring (500rpm) the absorption 15min.In 3min, drip the hydrogen peroxide solution of 4ml 25% gradually.With oil bath mixed solution is heated to 80 ℃ of afterreaction 1h behind the reaction 30min, utilizes magnet that magnetic microsphere is absorbed after the mixed solution cooling, remove supernatant, add deionized water then, repeat 3-10 time, be neutral until pH value of solution.Then with after the magnetic microsphere freeze drying that obtains.
Get the magnetic microsphere 0.5g for preparing above and be dispersed in the isopropanol water solution of 20ml90%, add the ammonia spirit of 10ml28%.Under stirring condition, drip the 1.0ml tetraethoxysilane then gradually.Behind stirring reaction 1h under the mixed solution normal temperature, with magnet magnetic microsphere is inhaled, then supernatant is outwelled, add deionized water once more, repeat 4-5 time and get final product.Then precipitation being carried out freeze drying preserves.
Get magnetic microsphere at N
2Following 500 ℃ of protection under burn 5h.Can obtain the magnetic hollow micro-nano ball after the taking-up.
The about 0.65 μ m of particle diameter of the magnetic hollow micro-nano ball that obtains by scanning electron microscopic observation.Utilize transmission electron microscope can observe microsphere surface and have uniform magnetic particle.The saturation magnetization of utilizing vibrating specimen magnetometer to record the magnetic hollow micro-nano ball is 36eum/g.
Embodiment 5
The poly (glycidyl methacrylate) microballoon that the surface of getting the 0.2g diameter and be 2.6 μ m has sulfonate radical is dispersed in the 20ml water, and is placed in the 100ml there-necked flask, feeds N
215min removes the oxygen in the system; Get 3.0m molFeCl
2Be dispersed in the 5ml water, and ultrasonic 5min is uniformly dispersed it; With Fe
2+Solution joins in the there-necked flask, adds 10% NaOH1.2ml behind stirring (500rpm) the absorption 15min.In 3min, drip the hydrogen peroxide solution of 4ml 28% gradually.With oil bath mixed solution is heated to 80 ℃ of afterreaction 1h behind the reaction 30min, utilizes magnet that magnetic microsphere is absorbed after the mixed solution cooling, remove supernatant, add deionized water then, repeat 3-10 time, be neutral until pH value of solution.Then with after the magnetic microsphere freeze drying that obtains.
Get the magnetic microsphere 0.1g for preparing above and be dispersed in the ethanolic solution of 20ml 90%, add the ammonia spirit of 2ml 28%.Under the condition that stirs (300rpm), drip the tetraethoxysilane ethanolic solution of 1ml 1g/ml then gradually.Behind stirring reaction 1h under the mixed solution normal temperature, with magnet magnetic microsphere is inhaled, then supernatant is outwelled, add deionized water once more, repeat 4-5 time and get final product.Then precipitation being carried out freeze drying preserves.
Get magnetic microsphere and heat 6h down at 300 ℃.Can obtain the magnetic hollow micro-nano ball after the taking-up.
Can observe microsphere surface by transmission electron microscope and have uniform magnetic particle, its structure also is a hollow-core construction.The saturation magnetization of utilizing vibrating specimen magnetometer to record the magnetic hollow micro-nano ball is 28eum/g.
Embodiment 6
The poly (methyl methacrylate) micro-sphere that the surface of getting 0.15g diameter 800nm has carboxylate radical is dispersed in the 150ml water, and is placed in the 100ml there-necked flask, feeds N
2Oxygen in the removal system; Get 1.0mmolFeCl
2Be dispersed in the 5ml water, and ultrasonic 5min is uniformly dispersed it; With Fe
2+Solution joins in the there-necked flask, adds 28% ammonia spirit 2ml behind stirring (300rpm) the absorption 15min.In 3min, drip the hydrogen peroxide solution of 2ml 25% gradually.With oil bath mixed solution is heated to 70 ℃ of afterreaction 1h behind the reaction 30min, utilizes magnet that magnetic microsphere is absorbed after the mixed solution cooling, remove supernatant, add deionized water then, repeat 3-10 time, be neutral until pH value of solution.Then with after the magnetic microsphere freeze drying that obtains.
Get the magnetic microsphere 0.1g for preparing above and be dispersed in the ethanolic solution of 10ml, add the ammonia spirit of 5ml 28%.Under stirring condition, drip the 0.5ml tetramethoxy-silicane then gradually.Behind stirring reaction 1h under the mixed solution normal temperature, with magnet magnetic microsphere is inhaled, then supernatant is outwelled, add deionized water once more, repeat 4-5 time and get final product.Then precipitation being carried out freeze drying preserves.
The magnetic microsphere of getting the above-mentioned preparation of 0.05g is at N
2The following 800 ℃ of following heating 2h of protection.Can obtain the magnetic hollow micro-nano ball.
The magnetic hollow micro-nano ball that obtains by transmission electron microscope observing is a hollow-core construction.The saturation magnetization of utilizing vibrating specimen magnetometer to record the magnetic hollow micro-nano ball is 29eum/g.
Claims (10)
1. a high molecular micro nanometer ball is the method that template prepares the magnetic hollow micro-nano ball, it is characterized in that, the high molecular micro nanometer ball that has negative electrical charge with the surface is a template, by generating with the magnetic nano-particle in the reaction of micro-nano ball surface in situ is shell, template particles is the magnetic microsphere of nuclear, further removes template by the method for burning and obtains the hollow magnetic micro-nano ball.
2. high molecular micro nanometer ball according to claim 1 is the method that template prepares the magnetic hollow micro-nano ball, it is characterized in that used macromolecule template micro-nano ball material is selected from one or more the combination in polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, poly hydroxy ethyl acrylate, poly (glycidyl methacrylate), polystyrene, PLA, polyethylene, polypropylene, the polyvinyl chloride.
3. high molecular micro nanometer ball according to claim 1 is the method that template prepares the magnetic hollow micro-nano ball, it is characterized in that, describedly prepares magnetic microsphere at the micro-nano ball surface in situ and adopts adsorption and oxidation method or coprecipitation.
4. high molecular micro nanometer ball according to claim 3 is the method that template prepares the magnetic hollow micro-nano ball, it is characterized in that, described adsorption and oxidation method is meant: in the template microsphere aqueous solution of 1-30mg/ml, at N
2Protection absorption quality down is the Fe of 0.1 times-1.0 times of template microsphere quality
2+Ion adds a spot of alkali lye and hydrogen peroxide then under stirring condition, make [OH
-]: [Fe
2+]=2-5, the amount of hydrogen peroxide is Fe
2+-1 times of 0.67 times of mole, behind the reaction 30min-60min, mixed solution is heated to 50 ℃-85 ℃ reaction 30min-2h, reaction finishes the back cooling, and this mixed liquor carried out Magnetic Isolation, the method of utilizing micro-nano hole to filter filters out the isolated magnetic particle of generation, then obtains pure magnetic composite microsphere.
5. high molecular micro nanometer ball according to claim 3 is the method that template prepares the magnetic hollow micro-nano ball, it is characterized in that, described coprecipitation is meant: in the template microsphere aqueous solution of 1-30mg/ml, add 1: 2 Fe of mol ratio
2+, Fe
3+Salting liquid, wherein the quality of Fe is 0.1 times-1.0 times of template microsphere, and feeds N
2Behind the deoxygenation 10min-30min, under mechanical agitation 300-800rpm, drip aqueous slkali gradually, final [OH
-]: [Fe
2+]=5-10, after dropwising reaction 10min-60min, mixed solution is heated to 50 ℃-85 ℃ reactions to be cooled off behind the 30min-2h, utilize magnet that the magnetic microsphere in the mixed solution is absorbed, remove supernatant, repeat 5 times-10 times, clarify until supernatant, till pH was neutrality, the method for utilizing micro-nano hole to filter filtered out the isolated magnetic particle of generation, then obtains pure magnetic microsphere.
6. be the method that template prepares the magnetic hollow micro-nano ball according to claim 1 or 3 or 4 or 5 described high molecular micro nanometer balls, it is characterized in that, described magnetic microsphere parcel one deck SiO
2
7. high molecular micro nanometer ball according to claim 6 is the method that template prepares the magnetic hollow micro-nano ball, it is characterized in that, described magnetic microsphere wraps up one deck SiO2 again, be specially: the pure water or the alcoholic solution that the magnetic microsphere of preparation are made into 1-30mg/ml, get this solution of 1ml, add the tetraethoxysilane of 1ml0.5-30mg/ml or the pure water or the alcoholic solution of tetramethoxy-silicane, 300-800rpm under the condition of mechanical agitation 300-800rpm then, in solution, add ammoniacal liquor or sodium hydroxide solution, wherein the consumption of alkali be make finally make the amount of OH-1 in the system be the silane substance amount 4-8 doubly, and make the reaction 20min-8h, then the solution that obtains is carried out Magnetic Isolation, solid drying is preserved.
8. high molecular micro nanometer ball according to claim 1 is the method that template prepares the magnetic hollow micro-nano ball, it is characterized in that, and described calcination, its temperature is 300 ℃-1000 ℃, the time is 5min-30h.
9. be the method that template prepares the magnetic hollow micro-nano ball according to claim 1 or 8 described high molecular micro nanometer balls, it is characterized in that, described calcination, its temperature is 300 ℃-800 ℃, the time is 20min-10h.
10. be the method that template prepares the magnetic hollow micro-nano ball according to claim 1 or 8 described high molecular micro nanometer balls, it is characterized in that, described calcination, its temperature is 300 ℃-700 ℃, the time is 40min-8h.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101552064B (en) * | 2008-12-16 | 2011-01-26 | 北京理工大学 | Method for preparing hollow magnetic ball |
| CN102976416A (en) * | 2012-12-04 | 2013-03-20 | 东华大学 | Preparation method of hollow superparamagnetic nanospheres |
| CN103483832A (en) * | 2013-09-16 | 2014-01-01 | 天津理工大学 | Preparation method for quasi-block copolymer inverse macromolecule micelle |
| CN109074508A (en) * | 2016-04-13 | 2018-12-21 | 京瓷株式会社 | RFID tag and RFID system |
-
2007
- 2007-10-18 CN CNA2007100471404A patent/CN101183588A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101552064B (en) * | 2008-12-16 | 2011-01-26 | 北京理工大学 | Method for preparing hollow magnetic ball |
| CN102976416A (en) * | 2012-12-04 | 2013-03-20 | 东华大学 | Preparation method of hollow superparamagnetic nanospheres |
| CN102976416B (en) * | 2012-12-04 | 2014-08-13 | 东华大学 | Preparation method of hollow superparamagnetic nanospheres |
| CN103483832A (en) * | 2013-09-16 | 2014-01-01 | 天津理工大学 | Preparation method for quasi-block copolymer inverse macromolecule micelle |
| CN103483832B (en) * | 2013-09-16 | 2015-07-22 | 天津理工大学 | Preparation method for quasi-block copolymer inverse macromolecule micelle |
| CN109074508A (en) * | 2016-04-13 | 2018-12-21 | 京瓷株式会社 | RFID tag and RFID system |
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